EP0032175B1 - Additifs pour huile lubrifiante, stables au cisaillement - Google Patents

Additifs pour huile lubrifiante, stables au cisaillement Download PDF

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Publication number
EP0032175B1
EP0032175B1 EP80107046A EP80107046A EP0032175B1 EP 0032175 B1 EP0032175 B1 EP 0032175B1 EP 80107046 A EP80107046 A EP 80107046A EP 80107046 A EP80107046 A EP 80107046A EP 0032175 B1 EP0032175 B1 EP 0032175B1
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EP
European Patent Office
Prior art keywords
weight
shear
lubricating oils
copolymer
styrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80107046A
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German (de)
English (en)
Other versions
EP0032175A2 (fr
EP0032175A3 (en
Inventor
Rainer Dr. Dipl.-Phys. Benda
Helmut Knöll
Peter Dr. Dipl.-Phys. Neudörfl
Horst Dr. Pennewiss
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP0032175A2 publication Critical patent/EP0032175A2/fr
Publication of EP0032175A3 publication Critical patent/EP0032175A3/de
Application granted granted Critical
Publication of EP0032175B1 publication Critical patent/EP0032175B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound

Definitions

  • the invention relates to shear-stable lubricating oil additives based on a combination of polyalkyl methacrylates (PAMA), olefin copolymers (OCP) and hydrogenated block copolymers, composed of conjugated dienes and styrene (HSD), in particular isoprene and styrene.
  • PAMA polyalkyl methacrylates
  • OCP olefin copolymers
  • HSD conjugated dienes and styrene
  • Lubricating oil additives are said to improve the viscosity index of the lubricating oils (VI improvers) and to have the best possible thickening, dispersing and detergent effect with simultaneous wear protection. Further critical points are the effect on the pour point and in particular the shear stability of the lubricating oil additives. An essential condition is that the mixtures with the mineral oils are stable systems. On the other hand, technology rightly expects commercial products with a high absolute polymer content to be made available.
  • polymers such as polyalkyl methacrylates (PAMA) and olefin copolymers (OCP), on which lubricating oil additives are generally based, have the desired qualities mentioned to varying degrees.
  • PAMA polyalkyl methacrylates
  • OCP olefin copolymers
  • German patent application DE-A 28 35 192.0 proposes lubricating oil additives based on a hydrogenated block copolymer of conjugated dienes and styrene (HSD), on which styrene and / or an alkyl ester of methacrylic acid, hydrophobizing vinyl esters and / or polymerizable heterocyclic additives are added Monomers are polymerized, styrene and / or the alkyl esters of (meth) acrylic acid being polymerized in the presence of the HSD in the first stage and the further monomers being grafted on in a second stage.
  • HSD conjugated dienes and styrene
  • Monomers are polymerized, styrene and / or the alkyl esters of (meth) acrylic acid being polymerized in the presence of the HSD in the first stage and the further monomers being grafted on in a second stage.
  • HSD conjugated dienes and styrene
  • Monomers are poly
  • olefin homopolymers or olefin copolymers known as VI improvers are dissolved in a medium suitable for use as a lubricant, for example mineral oil, to which dissolved olefin copolymer monomeric methacrylic acid esters, optionally together with other monomers known as building blocks of VI improvers, graft-polymerized and then admixed with the solution of a hydrogenated block copolymer composed of conjugated dienes and styrene in a suitable solvent.
  • the olefin homo- and in particular copolymers which can be used according to the invention are constructed in a known manner, preferably from ethylene, propylene, butylene or / and isobutylene.
  • w-phenyl-1-atkenes with 9 to 10 carbon atoms, norbornene (2), terminally unsaturated, unconjugated diolefins with 5 to 8 carbon atoms, dicyclopentadiene, 5-methylene norbornene (2) be co-polymerized.
  • Such olefin copolymers are known, for example, from DE-AS 644941, 1 963 039 and 1 042164 and from US Pat. Nos.
  • Olefin copolymers of ethylene / propylene with a propylene content of 25 to 60% by weight, preferably around 30% by weight, are particularly preferred. Their weight average molecular weights are generally in the range from 50,000 to 200,000.
  • the methacrylic acid esters are the esters used with an alcohol residue of 8-18 C atoms, preferably 10-18 C atoms; decyl, lauryl, palmityl, cetyl and stearyl esters or mixtures thereof may be mentioned in particular.
  • monomers can be used in smaller proportions, for example lower acrylic acid esters and methacrylic acid esters with 1-4 C atoms in the alcohol residue, such as. B. butyl acrylate and styrene, a-methylstyrene can be copolymerized.
  • the proportion of monomers which are not esters of C 8 -C 18 alcohols is from 0 to approx. 40%, based on the total acrylate / methacrylate component, including all other constituents.
  • the entirety of the monomers polymerized according to the invention in the presence of the polyolefin component is referred to below as the (meth) acrylate component.
  • monomers copolymerizable with the methacrylate component having polar or basic groups can be polymerized according to the invention.
  • a list of such monomers can be found, for example, in DE-A 26 34 033.
  • the polar or basic groups in the Experience has shown that monomers are suitable for imparting the desired dispersing-detergent action to the polymer.
  • monomers include, for example, dialkylaminoalkyl (meth) acrylates, in particular diethylaminoethyl methacrylate.
  • Polymerizable, heterocyclic monomers can also advantageously be copolymerized.
  • Vinylpyridine, vinylpyrrolidine, vinylpyrrolidone and / or vinylimidazole and their alkyl-substituted derivatives may be mentioned in particular.
  • the proportion of monomers with polar, in particular nitrogen-containing groups can be between 0 and 30%, preferably 0 and 10%, based on the proportion of acrylate or methacrylate (inciusive of the other non-polar or non-basic constituents).
  • the hydrogenated block polymers to be used according to the invention made up of conjugated dienes and styrene, are known, for example, from DE-A 21 56122. Hydrogenated block polymers of 2-methyl-1,3-butadiene (isoprene) and styrene are preferably used in a ratio of 55:45.
  • the hydrogenated block copolymers generally have an average molecular weight of 1,104 to 3,105, preferably 3 ⁇ 10 4 to 1 ⁇ 10 5 ; they are generally hydrogenated to a residual olefinic double bond content of ⁇ 15%, essentially ⁇ 5%.
  • the block copolymers can be prepared, for example, by anionic polymerization in aliphatic or cycloaliphatic solvents using alkali metals or organic compounds thereof.
  • the hydrogenation can also be carried out in a known manner, for example by catalytic hydrogenation over Raney nickel, platinum or palladium on carbon etc. or by means of reducing agents based on organometallic compounds, in particular hydrides.
  • the hydrogenated block polymer is composed of conjugated dienes and styrene, briefly referred to as “hydrogenated block polymer”.
  • the grafting up of the monomeric methacrylic acid esters and, if appropriate, further monomers of the (meth) acrylate component takes place in a medium suitable for later use as a lubricant, for example in a mineral oil, advantageously with a viscosity of 3-6 mPa.s at 100 ° C.
  • concentration of polyolefin in the medium suitable as a lubricant before the (grafting) polymerization of the methacrylate component begins is advantageously 5-20% by weight, preferably 10 to 15% by weight.
  • the polymerization of the methacrylate component can be carried out industrially largely based on known processes (see, for example, Pavlinec et al. J. Polymer Sc. Part C. No. 16, pp. 1113-1123 [1967]).
  • the polymerization can e.g. B. radical using suitable polymerization initiators, such as. B. per compounds, especially peracid esters.
  • suitable polymerization initiators such as. B. per compounds, especially peracid esters.
  • the appropriate amount of initiator in each case is within the knowledge of the person skilled in the art.
  • the solution of the hydrogenated block copolymer in a suitable solvent is then added to the solution obtained after the polymerization step.
  • a suitable solvent should meet the condition that it is able to dissolve both the styrene block and the diene block in the hydrogenated block polymer.
  • This condition is usually, e.g. B. of aromatic or aromatic residues containing solvents.
  • aromatic compounds without functional groups such as toluene, xylene and mineral oils with 10-40% aromatic content
  • further solvents with ester functions and aromatic radicals such as the esters of phthalic acid, especially dibutyl phthalate, and mixtures thereof, e.g. B. with mineral oil of about the type already used.
  • the concentration of the hydrogenated block polymer in the solvent is advantageously from 10 to 40% by weight, preferably from 15 to 30% by weight.
  • the components are preferably in the following ratio: olefin homo- or copolymer 5 to 25 parts by weight, (meth) acrylate component 40 to 70 parts by weight, hydrogenated block copolymers 5 to 55 parts by weight.
  • the ratio of olefin homo- or copolymer 10 to 20 parts by weight, (meth) acrylate component 50 to 70 parts by weight, hydrogenated block copolymers 10 to 40 parts by weight is particularly preferred.
  • the olefin homo- or. Copolymer can preferably be specified in the medium suitable for use as a lubricant together with at least one polymerization initiator.
  • the monomers of the (meth) acrylate component plus initiator to be polymerized are expediently heated, generally above 80 ° C., for example to 90 to 100 ° C. be metered in evenly over 3-4 hours with stirring.
  • a certain amount of initiator can be added.
  • the predetermined amount of initiator that is metered in with the monomers and the replenished amount can be in an approximate ratio of 2: 3: 1.
  • amounts of 0.1 to 3.0% by weight, based on the monomers to be polymerized, can be expected, the type of initiator and the other parameters of the batch having to be taken into account.
  • the hydrogenated block copolymers can then be added in a suitable solvent or solvent mixture of the type described above.
  • the end product then has a polymer content of about 37% by weight and contains about 26 parts by weight of methacrylate component, 4.55 parts by weight of olefin copolymer and 6.55 parts by weight of hydrogenated block copolymer per 100 parts by weight. Share solution.
  • the solutions obtained according to the invention are stable over at least the period required by the technology according to all the results available.
  • the polymer combinations obtained according to the invention are notable for their application. a. due to their particularly good shear stability.
  • the grafting is then carried out at 130 ° C., with a further 0.5 g of tert-butyl perbenzoate being added after 1 and 2 hours. Total grafting time 6 h.
  • Weight ratio of ethylene-propylene copolymer to polyalkyl methacrylate including polyvinylpyrrolidone 17/83.
  • Weight ratio of ethylene-propylene copolymer to polyalkyl methacrylate including polyvinylpyrrolidone and polyvinylimidazole 35/65.
  • Weight ratio of ethylene-propylene copolymer to hydrogenated isoprene-styrene block copolymer. to polyalkyl methacrylate including polyvinylpyrrolidone and polyvinylimidazole 22.5 / 37.5 / 40 .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (8)

1. Additifs stables au cisaillement pour huiles de graissage, sous forme de solutions convenant pour l'emploi direct, ayant une teneur élevée en polymères et contenant des homo- et/ou copolymères d'oléfines sur lesquels des méthacrylates ont été fixés par polymérisation par greffage, caractérisés en ce qu'ils sont obtenus par le fait que
a) l'on dissout les homo- et/ou copolymères d'oléfines, dans des proportions de 5 à 20 % en poids, dans un milieu susceptible d'être utilisé comme lubrifiant,
b) l'on fixe par polymérisation par greffage des méthacrylates monomères sur l'homo- et/ou le copolymère d'oléfine dissous et
c) l'on y ajoute la solution d'un copolymère séquencé hydrogéné d'isoprène et de styrène, en maintenant un rapport de l'homo- ou copolymère d'oléfine au méthacrylate et au copolymère séquencé hydrogéné d'isoprène et de styrène de 5-25 : 40-70 ; 5-55 parties en poids.
2. Additifs stables au cisaillement pour huiles de graissage selon la revendication 1, caractérisés en ce que les copolymères d'oléfines sont composés d'éthylène, de propylène, de butylène et/ou d'isobutylène.
3. Additifs stables au cisaillement pour huiles de graissage selon la revendication 1, caractérisés en ce qu'on fixe par polymérisation par greffage, sur l'homo- et/ou copolymère d'oléfines dissous, des méthacrylates dont le radical alcool contient 8 à 18 atomes de carbone et qui contiennent éventuellement, en plus faibles proportions, des acrylates et/ou méthacrylates inférieurs et/ou des monomères contenant des groupes polaires et/ou du styrène ou des dérivés polymérisables du styrène.
4. Additifs stables au cisaillement pour huiles de graissage selon l'une quelconque des revendications 1 à 3, caractérisés en ce que le rapport pondérai de l'homo- et/ou du copolymère d'oléfines dissous à l'ensemble des monomères qui doivent être fixés par polymérisation par greffage dans la phase (b) est de l'ordre de 5-40 95-60, de préférence de 5-20 : 95-80.
5. Additifs stables au cisaillement pour huiles de graissage selon la revendication 3, caractérisés en ce que la proportion des méthacrylates dont le radical alcool contient 8 à 18 atomes de carbone par rapport à la totalité des monomères qui doivent être fixés par polymérisation par greffage dans la phase (b) est de l'ordre de 60 à 100 % en poids, de préférence de 90 à 100 % en poids.
6. Additifs stables au cisaillement pour huiles de graissage selon la revendication 4 ou 5, caractérisés en ce que dans la phase (b), de la vinylpyridine et/ou de la vinylpyrrolidine et/ou de la vinylpyrrolidone et/ou du vinylimidazole sont fixés par polymérisation par greffage en plus faibles proportions.
7. Additifs stables au cisaillement pour huiles de graissage selon la revendication 1, caractérisés en ce que les copolymères séquencés hydrogénés qui sont mélangés dans la phase (c) sont composés de 2-méthyl-1,3-butadiène et de styrène.
8. Additifs stables au cisaillement pour huiles de graissage selon la revendication 7, caractérisés en ce que les copolymères séquencés hydrogénés sont dissous dans un solvant aromatique ou contenant des radicaux aromatiques, solvant qui peut encore contenir, le cas échéant, une huile minérale qui convient pour des additifs d'huiles de graissage.
EP80107046A 1980-01-12 1980-11-14 Additifs pour huile lubrifiante, stables au cisaillement Expired EP0032175B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3001045 1980-01-12
DE19803001045 DE3001045A1 (de) 1980-01-12 1980-01-12 Scherstabile schmieroeladditive

Publications (3)

Publication Number Publication Date
EP0032175A2 EP0032175A2 (fr) 1981-07-22
EP0032175A3 EP0032175A3 (en) 1981-10-07
EP0032175B1 true EP0032175B1 (fr) 1984-03-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP80107046A Expired EP0032175B1 (fr) 1980-01-12 1980-11-14 Additifs pour huile lubrifiante, stables au cisaillement

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EP (1) EP0032175B1 (fr)
DE (2) DE3001045A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3803406A1 (de) * 1988-02-05 1989-08-17 Roehm Gmbh Verfahren zur trennung von methanol-methylmethacrylat-mischungen

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4490267A (en) * 1982-12-31 1984-12-25 Shell Oil Company Preparation of a lubricating oil additive, an additive thus prepared _and a lubricating oil containing this additive
DE3930142A1 (de) * 1989-09-09 1991-03-21 Roehm Gmbh Dispergierwirksame viskositaets-index-verbesserer
US5416162A (en) * 1993-09-20 1995-05-16 Rohm And Haas Company Compatibilizer for a viscosity index improving polymer blend
US5663126A (en) 1994-10-21 1997-09-02 Castrol Limited Polar grafted polyolefins, methods for their manufacture, and lubricating oil compositions containing them
DE19502206A1 (de) * 1995-01-25 1996-08-01 Buna Sow Leuna Olefinverb Gmbh Funktionalisierte Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung in thermoplastischen Formmassen
ITMI20041672A1 (it) 2004-08-27 2004-11-27 Polimeri Europa Spa Copolimeri etilene-propilene a migliorata stabilita' di forma adatti alla modifica degli oli lubrificanti e procedimento per la loro preparazione
ES2666595T3 (es) * 2006-10-24 2018-05-07 Total Marketing Services Utilización de un fluido lubricante multifuncional

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772196A (en) * 1971-12-03 1973-11-13 Shell Oil Co Lubricating compositions
DE2603034C3 (de) * 1976-01-28 1982-04-15 Basf Ag, 6700 Ludwigshafen Mineralschmierölgemische
DE2740449C2 (de) * 1977-09-08 1986-08-21 Röhm GmbH, 6100 Darmstadt Verfahren zur Herstellung von Schmierölzusätzen
DE2835192C2 (de) * 1978-08-11 1986-12-11 Röhm GmbH, 6100 Darmstadt Schmieröladditive
DE2905954C2 (de) * 1979-02-16 1982-10-28 Röhm GmbH, 6100 Darmstadt Konzentrierte Polymerisatemulsionen als Viskositätsindexverbesserer für Mineralöle

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3803406A1 (de) * 1988-02-05 1989-08-17 Roehm Gmbh Verfahren zur trennung von methanol-methylmethacrylat-mischungen

Also Published As

Publication number Publication date
EP0032175A2 (fr) 1981-07-22
EP0032175A3 (en) 1981-10-07
DE3001045A1 (de) 1981-07-16
DE3067191D1 (en) 1984-04-26

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